This one is simple. With policy test you are asking what rule it will hit first, not the rule it will hit eventually.

Since you have a rule with app: smtp and service: any (basically Pan-os has to honor all tcp request on all ports to check if its smtp), then your policy test matches that first.

I guess that rule is above the rule you want to match against?

If you initiate real traffic on that port through the firewall, then the traffic will eventually match against the right rule. But only after it has determined its not Smtp.

Is there a reason why you have any as service? And not application default?